Fibre-reactive azo dyes containing vinylsulfonyl groups and further aliphatic fibre-reactive radicals

ABSTRACT

A reactive dye of the formula ##STR1## or of the formula ##STR2## or of the formula ##STR3## in which D, D 1  and D 2  are each phenylene or naphthylene unsubstituted or substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carboxylic acylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-β-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N-di-(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido hydroxyl, carboxyl, sulfomethyl, or sulfo, R 1  is hydrogen or C 1-4  -alkyl unsubstituted or substituted by halogen, hydroxyl, cyano, C 1-4  -alkoxy, methoxycarbonyl, ethoxycarbonyl, sulfamoyl, sulfato, carboxyl or sulfo, R 2  is (1) hydrogen, (2) alkyl unsubstituted or substituted by halogen, hydroxy, cyano, alkoxy, methoxycarbonyl, ethoxycarbonyl, sulfamoyl, sulferto, carboxy or sulfo, (3) cyclohexyl, (4) phenyl unsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, chlorine, bromine, carboxyl, sulfo or sulfomethyl, or (5) a radical of the formula --alk--SO 2  --Z, E--NH 2 , --CH 3 , --NH--CO--NH 2 , --NH--CO--CH 3  or --NH--CO--CH 2  --OH, wherein alk is C 2-6  --alkylene, Y is --SO 2  --Z, --SO 2  --N(R 1 )--Z, --N--(R 1 )--SO 2  --Z, --N(R 1 )--CO--(CH 2 ) 3-5  SO 2  --Z, --SO 2  --F, --SO 2  CH 2  --CH═CH 2 , --N(R 1 )--CO--CBr═CH 2 , --N(R 1 )--CO--CHBr--CH 2  Br, --N(R 1 )--CO--CCl═CH 2 , --N(R 1 )--CO--CHCl--CH 2  Cl, --N(R 1 )--CO--CH 2  Cl or --N(R 1 )--CO--CH═CH 2 , Z is --CH═CH 2  or --CH 2  CH 2  --A, A is --OSO 3  H, --SSO 3  H, --OCOCH 3 , --OPO 3  H 2 , --Cl, --Br or --F, and X is fluorine, chlorine or hydroxyl.

This application is a continuation application of application Ser. No.833,427, filed Feb. 24, 1986 (now abandoned), which application is inturn a continuation of application Ser. No. 664,142, filed Oct. 24, 1984(now abandoned).

The present invention relates to novel reactive dyes, to a process fortheir preparation, and to their use for dyeing and printing fibrematerials.

The practice of dyeing with reactive dyes has in recent years led toincreased demands on the quality of the dyeing and the economics of thedyeing process. There consequently continues to be a demand for newreactive dyes with improved properties, in particular applicationproperties.

The demand these days in the dyeing of cotton by the cold pad-batchmethod is for reactive dyes which are sufficiently substantive at thelow dyeing temperature and which also have good wash-off properties.They should also be highly reactive, so that only short batching timesare required, and they should in particular produce dyeings having highdegrees of fixation. Existing dyes meet these requirements only to aninsufficient degree.

It is therefore the object of the present invention to provide new,improved reactive dyes for the cold pad-batch method which have thequalities characterised above to a high degree. The new dyes should bedistinguished especially by high degrees of fixation and high fibre-dyebond stabilities, and the unfixed portions on the fibre should moreoverbe readily washed off. They should also produce dyeings having goodall-round fastness properties, for example light and wet fastnessproperties.

This object is achieved with the novel bireactive dyes definedhereinafter.

The invention accordingly provides reactive dyes of the formula ##STR4##in which D, D₁ and D₂ are each a phenylene or naphthylene radical whichcan be further substituted, R₁ is hydrogen or substituted orunsubstituted C₁₋₄ -alkyl, R₂ is hydrogen, substituted or unsubstitutedalkyl or aryl or a radical of the formula --alk--SO₂ --Z, E --NH₂,--CH₃, --NH--CO--NH₂, --NH--CO--CH₃ or --NH--CO--CH₂ --OH, alk is C₂₋₆-alkylene, Y is a --SO₂ --Z, --SO₂ --N(R₁)--Z, --N(R₁)--SO₂ --Z,##STR5## --SO₂ --F, --SO₂ --CH₂ --CH═CH₂, --N(R₁)--CO--CBr═CH₂,--N(R₁)--CO--CHBr--CH₂ Br, --N(R₁)--CO--CCl═CH₂, --N(R₁)--CO--CHCl--CH₂Cl, --N(R₁)--CO--CH₂ Cl or --N(R₁)--CO--CH═CH₂ radical, Z is a --CH═CH₂or --CH₂ CH₂ --A radical, A is an inorganic or organic radical which isdetachable under alkaline conditions, and X is fluorine, chlorine orhydroxyl.

The radicals D, D₁ and D₂ in the formulae (1), (2) and (2a) can befurther substituted in conventional manner. Examples of furthersubstituents are alkyl groups having 1 to 4 carbon atoms, such asmethyl, ethyl, propyl, isopropyl or butyl, alkoxy groups having 1 to 4carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy,acylamino groups having 1 to 8 carbon atoms, such as acetylamino,propionylamino or benzoylamino, amino, alkylamino having 1 to 4 carbonatoms, such as methylamino, ethylamino, propylamino, isopropylamino orbutylamino, phenylamino, N,N-di-β-hydroxyethylamino,N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such asmethoxycarbonyl or ethoxycarbonyl, alkylsulfonyl having 1 to 4 carbonatoms, such as methylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro,cyano, halogen, such as fluorine, chlorine or bromine, carbamoyl,N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, suchas N-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoylhaving 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl,N-propylsulfamoyl, N-isopropylsulfamoyl or butylsulfamoyl,N-(β-hydroxyethyl)-sulfamoyl, N,N-di-(β-hydroxyethyl)-sulfamoyl,N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.Preferred further substituents are methyl, ethyl, methoxy, ethoxy,acetylamino, benzoylamino, amino, chlorine, bromine, ureido, hydroxyl,carboxyl, sulfomethyl and sulfur. The radicals D, D₁ and D₂ preferablycontain one or more sulfo groups.

The alkyl radical R₁ can be straight-chain or branched and can also befurther substituted, for example by halogen, hydroxyl, cyano, C₁₋₄-alkoxy, carboxyl or sulfo. Examples of R₁ are: methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, carboxymethyl,β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, β-methoxyethyl, β-ethoxyethyl, β-methoxypropyl,β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl,β-cyanoethyl, sulfomethyl, β-sulfoethyl, aminosulfonylmethyl andβ-sulfatoethyl. R₁ is preferably hydrogen, methyl or ethyl.

The radical R₂ can be for example an alkyl radical which isstraight-chain or branched, which preferably has 1 to 6 carbon atoms andwhich can be further substituted, for example by halogen, hydroxyl,cyano, alkoxy, carboxyl or sulfo, or an unsubstituted alkyl radicalhaving 7 to 20 carbon atoms, a cyclohexyl radical, or a phenyl radicalwhich can be substituted, for example by methyl, ethyl, methoxy, ethoxy,chlorine, bromine, carboxyl, sulfo or sulfomethyl. Examples of R₂ arethe following substituents: methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec.-butyl, tert.-butyl, pentyl, hexyl, nonyl, dodecyl,hexadecyl, pentadecyl, carboxymethyl, β-carboxyethyl, β-carboxypropyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxyethyl,β-ethoxyethyl, β-methoxypropyl, β-chloroethyl, γ-chloropropyl,γ-bromopropyl, sulfomethyl, β-sulfoethyl, aminosulfonylmethyl,β-sulfatoethyl, cyclohexyl, phenyl, o-, m- or p-chlorophenyl, o-, m- orp-methylphenyl, p-ethylphenyl, p-methoxyphenyl, o-, m- or p-sulfophenyl,p-carboxyphenyl and p-sulfomethylphenyl. R₂ is preferably hydrogen or aradical of the formula --alk--SO₂ --Z.

In the event that R₂ is a radical of the formula --alk--SO₂ --Z, the tworadicals which are bonded to the nitrogen atom in question can beidentical or different. The two radicals of the formula --alk--SO₂ --Zare preferably identical.

The bridge member alk is a straight-chain or branched alkylene radicalhaving 2 to 6 carbon atoms, for example ethylene, n-propylene,isopropylene, n-butylene, n-pentylene or n-hexylene. alk is preferablyan ethylene radical.

The inorganic or organic radical which can be detached under alkalineconditions can be one of the following anionically detachable groups:##STR6##

Examples of Y are β-sulfatoethylsulfonyl, vinylsulfonyl,β-sulfatoethylaminosulfonyl, N-methyl-N-β-sulfatoethylaminosulfonyl,N-ethyl-N-β-sulfatoethylaminosulfonyl, β-chloroethylsulfonyl,chloroacetylamino, α,β-dichloropropionylamino,α,β-dibromopropionylamino, α-bromoacryloylamino and4-(β-chloroethylsulfonyl)-butyrylamino. Y is preferablysulfatoethylsulfonyl or vinylsulfonyl.

Examples of the radical --N(R₂)--alk--SO₂ --Z areβ-(β-chloroethylsulfonyl)-ethylamino,γ-(β-chloroethylsulfonyl)-propylamino,bis-[β-(β-chloroethylsulfonyl)-ethyl]-amino,N-methyl-N-β-(β-chloroethylsulfonyl)-ethylamino,N-phenyl-N-β-(β-chloroethylsulfonyl)-ethylamino,β-vinylsulfonyl-ethylamino, bis(β-vinylsulfonyl-ethyl)-amino,N-β-sulfatoethyl-N-β-(β-chloroethylsulfonyl)-ethylamino,β-(β-sulfatoethylsulfonyl)-ethylamino,δ-(β-chloroethylsulfonyl)-butyrylamino and δ-vinylsulfonyl-butytylamino.Preference is given to β-(β-chloroethylsulfonyl)-ethylamino andβ-vinylsulfonyl-ethylamino.

The substituent X is in particular chlorine and especially fluorine.

Preference is given to: reactive dyes of the formula ##STR7## in whichR₃ is hydrogen, methyl or ehtyl, R₄ is hydrogen or a --alk--SO₂ --Zradical, alk is C₂₋₆ -alkylene, Y is a --SO₂ --Z radical, Z is a--CH═CH₂ or --CH₂ CH₂ --A radical, A is sulfato, acetoxy, chlorine,phosphato or thiosulfato, and X is fluorine, chlorine or hydroxyl;reactive dyes of the formula ##STR8## in which R₅ is hydrogen or a--alk--SO₂ --Z radical, alk is C₂₋₆ -alkylene, Y is a --SO₂ --Z radical,Z is a --CH═CH₂ or --CH₂ CH₂ --A radical, A is sulfato, acetoxy,chlorine, phosphato or thiosulfato, and X is fluorine, chlorine orhydroxyl; reactive dyes of the formula ##STR9## in which R₆ is hydrogenor a --alk--SO₂ --Z radical, alk is C₂₋₆ -alkylene, Y is a --SO₂ --Zradical, Z is a --CH═CH₂ or --CH₂ --CH₂ --A radical, A is sulfato,acetoxy, chlorine, phosphato or thiosulfato, and X is fluorine, chlorineor hydroxyl; reactive dyes of the formulae ##STR10## in which R₇ ishydrogen or a --alk--SO₂ --Z radical, alk is C₂₋₆ -alkylene, Y is a--NH--CO+CHBr--CH₂ --Br, --NH--CO--CBr═CH₂ or --SO₂ --Z radical, Z is a--CH═CH₂ or --CH₂ --CH₂ --A radical, A is sulfato, acetoxy, chlorine,phosphato or thiosulfato, X is fluorine, chlorine or hydroxyl, E is--NH₂, --CH₃, --NH--CO--NH₂ or --NH--CO--CH₃, and one V is is OH theother V is NH₂ ; the reactive dye of the formula ##STR11##

The process for preparing the reactive dyes of the formulae (1), (2) or(2a) comprises reacting dyes of the formulae ##STR12## or theirprecursors with reactive components to introduce the radicals of theformula ##STR13## to give reactive dyes of the formula (1), (2) or (2a),or converting the intermediates obtained into the desired end dyes, andif desired immediately carrying out a further conversion.

The introduction of the radical Y and of the radical of the formula (12)into the dye of the formula (10), (10a) or (11) is effected in a mannerknown per se, for example through acylation with appropriate carboxylicacid halides or anhydrides and condensation with cyanuric halides andamines of the formula

    HN(R.sub.2)--alk--SO.sub.2 --Z                             (13).

In the event that Y is a radical which is bonded via a --N(R₁)-- aminogroup, D or D₁ must contain such an amino group. In this case, the diazocomponent is a diamine or a corresponding amino acetylamino or aminonitro compound in which the acetylamino and nitro groups are convertedbefore the condensation with the acylating agent into the NH₂ group byhydrolysis and reduction respectively. If, however, Y is a directlybonded sulfonyl radical, the starting material used is a precursor whichalready contains this radical, for example1-amino-4-β-sulfatoethylsulfonylbenzene as diazo component. Thereactions required for preparing the end dyes from precursors arecouplings or conversions to the reactive radicals.

As the individual process steps given above can be carried out indifferent orders, there are a number of possible versions for theprocess. In general the overall reaction is carried out in successivesteps, and the order of the elementary reactions between the individualreactants is advantageously arranged in accordance with the specialconditions. As a fluorotriazine radical can hydrolyse under certainconditions, an intermediate which contains acetylamino groups must behydrolysed to split off the acetyl groups before it is condensed with anaminodifluorotriazine or trifluorotriazine. Which reaction isadvantageously carried out first in preparing a secondary condensationproduct from an HN(R₂)--alk--SO₂ --Z amine, 2,4,6-trifluoro-s-triazineand diaminobenzenesulfonic acid, that of the trifluorotriazine with theamine or that with the diaminobenzenesulfonic acid, varies from case tocase and mainly depends on the solubility of the amino compoundsinvolved and on the basicity of the amino groups to be acylated.

In one embodiment, for example, a diazo component which contains anacylatable --N(R₁)H group is acylated with an acyl halide, the reactionproduct is diazotised and coupled onto a coupling component whichcontains a --N(R₁)H group, and the resulting monoazo compound iscondensed with an aminodihalogenotriazine of the formula ##STR14## inwhich X is fluorine or chlorine or acylated with atrihalogeno-s-triazine, and the product is subsequently condensed withan amine of the formula (13).

Another method comprises first of all preparing a dye which contains aprecursor of the reactive radical and then converting this precursorinto the reactive radical itself, for example by esterification or anaddition reaction. For example, it is possible to prepare a dye in whichY contains an HO--CH₂ CH₂ -- radical and to react the intermediatebefore or after the acylation with sulfuric acid, so that the hydroxylgroup is converted into the sulfato group; or to use an analogous dye inwhich Y contains the H₂ C═CH-- vinyl group, and to add the intermediateonto thiosulfuric acid, producing an HO₃ SS--CH₂ CH₂ -- radical.

The hydroxyl group in a dye of the formula (10) or (11) or in a suitableprecursor is preferably sulfated by reaction at 0° C. to moderatelyelevated temperatures with concentrated sulfuric acid. This sulfationcan also be effected by reacting the hydroxy compound at 10° to 80° C.with 2 equivalents of chlorosulfonic acid per hydroxyl group in a polarorganic solvent, for example N-methylpyrrolidone. The sulfation ispreferably effected by adding the compound in question to sulfuric acidmonohydrate at temperatures between 5° and 15° C. In the subsequentsulfation a fluorine atom on the triazine ring can be replaced by ahydroxyl group.

The introduction into a compound of the formula (1) or an intermediateof an inorganic or organic radical X which is detachable under alkalineconditions, other than a halogen atom or the sulfato group, for examplea thiosulfato or phosphato group, is effected in a manner known per se.

Moreover, the synthesis can be followed by elimination reactions. Forexample, reactive dyes of the formula (1) which containsulfatoethylsulfonyl radicals can be treated with agents which eliminatehydrogen halide, such as sodium hydroxide, to convert thesulfatoethylsulfonyl radicals into vinylsulfonyl radicals. Or, in theevent that in a reactive dye of the formula (1) the radical Y is anα,β-dibromopropionylamino radical, the α,β-dibromopropionyl group, bytreatment with agents which eliminate hydrogen halide, can be convertedinto the α-bromoacryloyl group, if desired at the same time as theabovementioned elimination of sulfuric acid from a sulfatoethylsulfonylradical.

The above-described way of synthesis via an intermediate of the reactiveradical is in many cases uniform and complete.

The dyes of the formulae (10) or (11) or the dye precursors are acylatedwith acyl halides or halogenotriazines in manners known per se,preferably in aqueous solutions or suspensions and in the presence ofalkaline, acid-binding agents, for example aqueous alkali metalhydroxides, carbonates or bicarbonates.

Reactive dyes of the formula (1) in which Y is a directly bondedsulfonyl radical can be prepared by starting from dyes of the formulae(10) or (11) which already contain a Y group, and acylating the --N(R₁)Hgroup with a halogenotriazine, or using appropriate precursors, forexample a diazo component of the formula ##STR15## and coupling it ontoa coupling component which contains a --N(R₁)H group, and acylating the--N(R₁)H group with a halogenotriazine before or after the coupling.

If the synthesised reactive dyes contain groups capable of metal complexformation, the reactive dyes can also be subsequently metallised.

The most important versions of the process are described in theillustrative embodiments.

There now follow specific examples of starting materials which can beused for preparing the reactive dyes of the formula (1).

DIAZO COMPONENTS

1,3-diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene,1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene,1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene,1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene,1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene,1,4-diamino-2,5-diethoxybenzene, 2,6-diaminonaphthalene,1,3-diamino-2,4,6-trimethylbenzene,1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene,4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl(benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine,3,3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine,4,2'-diaminodiphenyl (diphenylene),2,6-diaminonaphthalene-4,8-disulfonic acid,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diaminobenzene-2,6-disulfonic acid,1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonicacid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid,1,4-diamino-2-methylbenzene-5-sulfonic acid,1,5-diamino-6-methylbenzene-3-sulfonic acid,1,3-diamino-6-methylbenzene-4-sulfonic acid, 3-(3'- or4'-aminobenzoylamino)-1-aminobenzene-6-sulfonic acid,1-(4'-aminobenzoylamino)-4-aminobenzene-2,5-disulfonic acid,1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylicacid, 1,2-diaminobenzene-4-carboxylic acid,1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino- 2-methylbenzene,4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulfonicacid, 4,4'-diaminodiphenyloxyethan-2,2'-disulfonic acid,4,4'-diaminostilbene-2,2'-disulfonic acid,4,4'-diaminodiphenylethane-2,2'-disulfonic acid,2-amino-5-aminomethylnaphthalene-1-sulfonic acid,2-amino-5-aminomethylnaphthalene-1,7-disulfonic acid and1-amino-4-methoxy-5-aminomethylbenzene-6-sulfonic acid.

If the diazo component to be used is not a diamine but anaminoacetylamino compound from which the acetyl is subsequently to bereeliminated by hydrolysis, as mentioned above in the description of theprocess variants, the monoacetyl compounds of the abovementioned diazocompounds are possible, examples being1-acetylamino-3-aminobenzene-4-sulfonic acid and1-acetylamino-4-aminobenzene-3-sulfonic acid. Examples of diazocomponents which already contain a Y group are 1-amino-2-, -3- or-4-β-sulfoethylsulfonylbenzene,1-amino-3-β-phosphatoethylsulfonylbenzene,1-amino-4-methyl-3-β-sulfatoethylsulfonylbenzene,1-amino-3-β-chloroethylsulfonylbenzene,1-amino-4-methoxy-3-β-sulfatoethylsulfonylbenzene,1-amino-4-β-sulfatoethylsulfonylbenzene-2-sulfonic acid,1-amino-5-β-sulfatoethylsulfonylbenzene-2-sulfonic acid,1-amino-5-β-sulfatoethylsulfonylbenzene-2,4-disulfonic acid,1-amino-4-β-sulfatoethylsulfonylnaphthalene,1-amino-2,5-dimethoxy-4-β-sulfatoethylsulfonylbenzene,1-amino-4-β-sulfatoethylsulfonylbenzene-2-carboxylic acid,1-amino-5-β-sulfatoethylsulfonylbenzene-2-carboxylic acid,1-amino-2-methoxy-4-β-sulfatoethylsulfonylbenzene,1-amino-2-chloro-4-β-sulfatoethylsulfonylbenzene,1-amino-2-methoxy-5-β-sulfatoethylsulfonylbenzene,2-amino-8-β-sulfatoethylsulfonylnaphthalene,2-amino-8-β-sulfatoethylsulfonylnaphthalene-6-sulfonic acid,1-amino-2,5-dimethoxy-4-vinylsulfonylbenzene,1-amino-2-methoxy-5-methyl-4-β-sulfatoethylsulfonylbenzene,1-amino-2,5-diethoxy-4-β-sulfatoethylsulfonylbenzene,1-amino-2-bromo-4-β-sulfatoethylsulfonylbenzene,1-amino-2-bromo-4-vinylsulfonylbenzene,1-amino-5-vinylsulfonylbenzene-2,4-disulfonic acid,1-amino-5-β-phosphatoethylsulfonylbenzene-2,4-disulfonic acid,1-amino-5-β-chloroethylsulfonylbenzene-2,4-disulfonic acid,2-amino-8-β-phosphatoethylsulfonylnaphthalene-6-sulfonic acid,2-amino-8-vinylsulfonylnaphthalene-6-sulfonic acid,1-amino-2-methoxy-5-methyl-4-β-chloroethylsulfonylbenzene,2-amino-4-β-sulfatoethylsulfonylphenol, 1-amino-3- or-4-vinylsulfonylbenzene,1-amino-2-hydroxy-4-β-sulfatoethylsulfonylbenzene,1-amino-5-vinylsulfonylbenzene-2-sulfonic acid,3-(N-methyl-β-sulfatoethylsulfonylamino)-1-aminobenzene,3-(N-ethyl-β-sulfatoethylsulfonylamino)-1-aminobenzene and3-β-sulfatoethylsulfonylamino-1-aminobenzene.

COUPLING COMPONENTS

1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-8-hydroxynaphthalene-4,6-disulfonic acid,1-amino-8-hydroxynaphthalene-4-sulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-methylamino-5-hydroxynaphthalene-7-sulfonic acid,2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid,2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7-sulfonic acid,1-(4'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulfonicacid, 1-(4'-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or-4,6-disulfonic acid, 1-(3'-aminobenzoylamino)-8-hydroxynaphthalene-3,6-or -4,6-disulfonic acid,1-(3'-nitrobenzoylamino)-8-hydroxynaphthalene-3,6- or 4,6-disulfonicacid, 2-(4'-amino-3'-sulfophenylamino)-5-hydroxynaphthalene-7-sulfonicacid, 1,3-diaminobenzene-4-sulfonic acid, 1-amino-3-methylbenzene,1-amino-3-carbamoyl-aminobenzene, 1-amino-3-acetylaminobenzene and1-amino-3-hydroxyacetylaminobenzene.

REACTIVE COMPONENTS

The halides of the abovementioned Y radicals, for exampleα,β-dibromopropionyl chloride, α,β-dichloropropionyl chloride,α-bromoacryloyl chloride or α-chloroacryloyl chloride, if desired alsosimilarly reacting halogenated anhydrides, such as α,β-dichloropropionicanhydride, 4-(β-chloroethylsulfonyl)-butyryl chloride,4-vinylsulfonylbutyryl chloride and the like, 2,4,6-trifluoro-s-triazine(cyanuric fluoride) and 2,4,6-trichloro-s-triazine (cyanuric chloride),as well as the primary condensation products of2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-s-triazine with the aminesof the formula (13) mentioned hereinafter.

AMINES OF THE FORMULA (13)

β-(β-Chloroethylsulfonyl)-ethylamine,β-(β-bromoethylsulfonyl)-ethylamine, β-vinylsulfonyl-ethylamine,γ-(β-chloroethylsulfonyl)-propylamine,α-(β-chloroethylsulfonyl)-isopropylamine,δ-(β-chloroethylsulfonyl)-butylamine,β-(β-chloroethylsulfonyl)-isobutylamine,ε-(β-chloroethylsulfonyl)-pentylamine,β-(β-chloroethylsulfonyl)-hexylamine,N-methyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-ethyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-propyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-butyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-pentyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-hexyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-nonyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-dodecyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-hexadecyl-N-β-(β-chloroethyl)-ethylamine,N-octadecyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-carboxymethyl-N-β-(β-bromoethylsulfonyl)-ethylamine,N-sulfatomethyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-β-carboxyethyl-N-γ-(β-chloroethylsulfonyl)-propylamine,N-β-sulfatoethyl-N-γ-(β-chloroethylsulfonyl)-propylamine,N-β-sulfatoethyl-N-δ-(β-chloroethylsulfonyl)-butylamine,N-β-ethoxyethyl-N-δ-(β-chloroethylsulfonyl)-butylamine,N-γ-chloropropyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-phenyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-p-chlorophenyl-N-β-(β-chloroethylsulfonyl)-ethylamine,N-o-methylphenyl-N-β(β-chloroethylsulfonyl)-ethylamine,N-p-methoxyphenyl-N-β(β-chloroethylsulfonyl)-ethylamine,N-m-sulfophenyl-N-β(β-chloroethylsulfonyl)-ethylamine,N-p-sulfophenyl-N-β-(β-chloroethylsulfonyl)-ethylamine,bis-[β-(β-chloroethylsulfonyl)-ethyl]-amine,bis-[β-(β-bromoethylsulfonyl)-ethyl]-amine,bis-[γ-(β-chloroethylsulfonyl)-propyl]-amine,bis-[δ-(β-chloroethylsulfonylbutyl]-amine, andbis-(β-vinylsulfonylethyl)-amine.

Preference is given to amines of low molecular weight, such asβ-(β-chloroethylsulfonyl)-ethylamine and its N-methyl derivative.Bis-[β-(β-chloroethylsulfonyl)-ethyl]-amine is particularly preferred.

Examples of possible dyes of the formulae (10) and (11) are dyes of thefollowing structural groups: ##STR16## metal complexes of dyes of theformulae ##STR17## The metal atom is preferably Cu (1:1 complex) or Crand Co (1:2 complex). Cr- and Co-complexes can contain one or twomolecules of the azo compound of the abovementioned formula, i.e. theycan be symmetrical or include any other ligand group and beasymmetrical. ##STR18## The fused rings indicated by the broken linesstand for alternatively possible naphthalene systems.

The dyes of the abovementioned formulae can be further substituted inthe alkyl or aryl radicals, in particular by the substituents mentionedin the explanation of the formula (1). ##STR19## and the metal complexazo dyes of the formulae ##STR20##

The diazotisation of the diazo components and of the intermediatescontaining a diazotisable amino group is generally effected through theaction of nitrous acid in aqueous mineral acid solutions at lowtemperatures. The coupling onto the coupling component is effected atstrongly acid, neutral or weakly alkaline pH.

The condensation of the reactive components with the diazo componentsand coupling components and with the amines or with acylatable monoazoor disazo intermediates or with the amino-containing dyes is preferablyeffected in aqueous solutions or suspensions, at low temperatures and atweakly acid, neutral or weakly alkaline pH. The hydrogen halide set freein the course of the condensation is advantageously continuouslyneutralised by adding aqueous alkali metal hydroxides, carbonates orbicarbonates.

The reactive dyes of the formula (1) are fibre-reactive. Fibre-reactivecompounds are to be understood as meaning compounds which are capable ofreacting with the hydroxyl groups of the cellulose or with the aminogroups of natural or synthetic polyamides to form covalent chemicalbonds.

The reactive dyes of the formula (1) are suitable for dyeing andprinting a very wide variety of different materials, such as silk,leather, wool, nylon fibres and polyurethanes, and in particularcellulose-containing fibre materials of any kind. Examples of thesefibre materials are natural cellulose fibres, such as cotton, linen andhemp, pulp and regenerated cellulose. The reactive dyes of the formula(1) are also suitable for dyeing or printing hydroxyl-containing fibrespresent in blend fabrics, for example blends of cotton with polyesterfibres or nylon fibres.

The dyes according to the invention can be applied to the fibrematerial, and be fixed on the fibre, by various methods, in particularin the form of aqueous dye solutions and print pastes. They are suitablenot only for the exhaust method but also for dyeing by the pad-dyeingmethod, whereby the cloth is impregnated with aqueous dye solutionswhich can contain salt, and the dyes are fixed after an alkali treatmentor in the presence of alkali, if desired under heat. They areparticularly suitable for the so-called cold pad-batch method, wherebythe dye is applied on the pad-mangle together with the alkali and isthen fixed by leaving the padded cloth to stand at room temperature forseveral hours. After the dye has been fixed the dyeings or prints arethoroughly rinsed with cold and hot water in the presence or absence ofan agent which acts like a dispersant and promotes the diffusion of theunfixed portions.

The reactive dyes of the formula (1) are distinguished by highreactivity and good fixing properties. For this reason they can be usedfor exhaust dyeing at low dyeing temperatures and only short steamingtimes are necessary in the pad-steam process. The degrees of fixationare high, and the unfixed portions are readily washed off, thedifference between the degree of exhaustion and degree of fixation beingremarkably small, i.e. the hydrolysis loss is very small. The reactivedyes of the formula (1) are also suitable for printing, in particular oncotton, but also for printing nitrogen-containing fibres, for examplewool, silk or wool-containing blend fabrics.

The dyeings and prints prepared with the dyes according to the inventionon cellulose fibre materials have a high tinctorial strength and a highfibre-dye bond stability, both in the acid range and the alkaline range,plus a good light fastness and very good wet fastness properties, suchas wash, water, seawater, cross-dyeing and perspiration fastnessproperties, and good pleating fastness, hot-press fastness and rubfastness.

The following examples serve to illustrate the invention. Thetemperatures are given in degrees centigrade, and the parts andpercentages are by weight unless otherwise stated. Parts by weightrelate to parts by volume as the kilogram relates to the liter.

The preparation of the monoazo or disazo intermediate compounds has notbeen described in all cases in the following illustrative embodiments,but it is readily apparent from the general description.

EXAMPLE 1

31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid aredissolved in 100 parts of water under neutral conditions. This solutionis added dropwise in the course of 10 minutes to a mixture of 200 partsof ice and water, 18.5 parts of 2,4,6-trichloro-1,3,5-triazine and 10parts of 37% hydrochloric acid. The reaction mixture is held at pH 1.5until the condensation has ended by continuously adding 2N sodiumhydroxide solution. After the addition of 22.9 parts ofβ-(β-chloroethylsulfonyl)-ethylamine hydrochloride, the temperature ofthe reaction mixture is gradually raised from 5° C. to 20° C., while thereaction mixture is initially held at pH 6.5 and then at pH 8.0 by thecontinuous addition of 2N sodium hydroxide solution. After thecondensation and elimination reaction has ended, this dye intermediateis coupled at 0° to 10° C. and pH 6.0 with 28.1 parts of diazotised1-amino-4-(β-sulfatoethylsulfonyl)-benzene. After the coupling reactionat pH 6.5 has ended, the reaction mixture is clarified and the resultingreactive dye of the formula ##STR21## is salted out by sprinkling inpotassium chloride, is filtered off and is dried in vacuo. It dyescotton in red shades.

Other useful reactive dyes which dye cotton in the hues given in column4 of Table 1 are obtained by following Example 1 and reacting1-amino-8-hydroxynaphthalene-3,6-disulfonic acid first with2,4,6-trichloro-1,3,5-triazine and then with the amino compoundindicated in column 2 and coupling the diazotised diazo componentindicated in column 3 onto the coupling component thus obtained.

If desired the isolation of the dye at pH 6.5-7.5 can be preceded by anelimination reaction in which the reaction solution is held at 15° to25° C. at pH 9.0-10.0 by the continuous addition of 2N sodium hydroxidesolution until complete conversion is indicated by chromatography.

                                      TABLE 1                                     __________________________________________________________________________                                   Hue on                                         No.                                                                              Amino compound                                                                             Diazo component                                                                              cotton                                         __________________________________________________________________________    1  β-(β-Chloroethylsulfonyl)-                                                       1-amino-3-(β-sulfatoethyl-                                                              yellowish                                         ethylamine hydrochloride                                                                   sulfonyl)-benzene                                                                            red                                            2  β-(β-Chloroethylsulfonyl)-                                                       1-amino-2-(β-sulfatoethyl-                                                              red                                               ethylamine hydrochloride                                                                   sulfonyl)-benzene                                             3  β-(β-Chloroethylsulfonyl)-                                                       1-amino-4-allylsulfonyl-                                                                     red                                               ethylamine hydrochloride                                                                   benzene                                                       4  β-(β-Chloroethylsulfonyl)-                                                       1-amino5-(2,3-dibromo-                                                                       yellowish                                         ethylamine hydrochloride                                                                   propionylamino)-benzene-                                                                     red                                                            2-sulfonic acid                                               5  β-(β-Chloroethylsulfonyl)-                                                       1-amino-5-(α-bromoacryloyl-                                                            yellowish                                         ethylamine hydrochloride                                                                   amino)-benzene-2-sulfonic                                                                    red                                                            acid                                                          6  β-(β-Chloroethylsulfonyl)-                                                       1-amino-5-(2,3-dichloro-                                                                     yellowish                                         ethylamine hydrochloride                                                                   propionylamino)-benzene-2-                                                                   red                                                            sulfonic acid                                                 7  β-(β-Chloroethylsulfonyl)-                                                       1-amino-5-chloroacetylamino-                                                                 yellowish                                         ethylamine hydrochloride                                                                   benzene-2-sulfonic acid                                                                      red                                            8  Bis-(β-(β-chloroethyl-                                                           1-amino-4-(β-sulfatoethyl-                                                              red                                               sulfonyl)-ethyl)-amine                                                                     sulfonyl)-benzene                                                hydrochloric acid                                                          9  Bis-(β-(β-chloroethyl-                                                           1-amino-2-(β-sulfatoethyl-                                                              red                                               sulfonyl)-ethyl)-amine                                                                     sulfonyl)-benzene                                                hydrochloric acid                                                                          sulfonyl)-benzene                                             10 Bis-(β-(β-chloroethyl-                                                           1-amino-4-allysulfonyl-                                                                      red                                               sulfonyl)-ethyl)-amine                                                                     benzene                                                          hydrochloric acid                                                          11 Bis-(β-(β-chloroethyl-                                                           1-amino-5-(2,3-dibromo-                                                                      yellowish                                         sulfonyl)-ethyl)-amine                                                                     propionylamino)-benzene-2-                                                                   red                                               hydrochloric acid                                                                          sulfonic acid                                                 12 Bis-(β-(β-chloroethyl-                                                           1-amino-5-(2,3-dichloro-                                                                     yellowish                                         sulfonyl)-ethyl)-amine                                                                     propionylamino)-benzene-2-                                                                   red                                               hydrochloric acid                                                                          sulfonic acid                                                 13 Bis-(β-(β-chloroethylsulfo-                                                      1-amino-5-chloroacetyl-                                                                      yellowish                                         nyl)-ethyl)-amine hydro-                                                                   amino-benzene-2-sulfonic                                                                     red                                               chloride acid                                                              14 Bis-(β-(β-chloroethylsulfo-                                                      1-amino-3-(β-sulfatoethyl-                                                              yellowish                                         nyl)-ethyl)-amine hydro-                                                                   sulfonyl)-benzene                                                                            red                                               chloride acid                                                              15 3-(β-Chloroethylsulfonyl)-                                                            1-amino-4-(β-sulfatoethyl-                                                              red                                               propylamine hydrochloride                                                                  sulfonyl)-benzene                                             16 3-(β-Chloroethylsulfonyl)-                                                            1-amino-3-(β-sulfatoethyl-                                                              yellowish                                         propylamine hydrochloride                                                                  sulfonyl)-benzene                                                                            red                                            17 3-(β-Chloroethylsulfonyl)-                                                            1-amino-2-(β-sulfatoethyl-                                                              red                                               propylamine hydrochloride                                                                  sulfonyl)-benzene                                             18 3-(β-Chloroethylsulfonyl)-                                                            1-amino-5-(2,3-dibromo-                                                                      yellowish                                         propylamine hydrochloride                                                                  propionylamino)-benzene-2-                                                                   red                                                            sulfonic acid                                                 19 4-(β-Chloroethylsulfonyl)-                                                            1-amino-4-(β-sulfatoethyl-                                                              red                                               butylamine hydrochloride                                                                   sulfonyl)-benzene                                             20 4-(β-Chloroethylsulfonyl)-                                                            1-amino-3-(β-sulfatoethyl-                                                              yellowish                                         butylamine hydrochloride                                                                   sulfonyl)-benzene                                                                            red                                            21 4-(β-Chloroethylsulfonyl)-                                                            1-amino-2-(β-sulfatoethyl-                                                              red                                               butylamine hydrochloride                                                                   sulfonyl)-benzene                                             22 4-(β-Chloroethylsulfonyl)-                                                            1-amino-5-(2,3-dibromo-                                                                      yellowish                                         butylamine hydrochloride                                                                   propionylamino)-benzene-2-                                                                   red                                                            sulfonic acid                                                 23 β-(β-Chloroethylsulfonyl)-                                                       1-amino-5-(4-(β-chloroethyl-                                                            yellowish                                         ethylamine hydrochloride                                                                   sulfonyl)-butyrylamino)-                                                      benzene-2-sulfonic acid                                       24 Bis-(β-(β-chloroethylsulfo-                                                      1-amino-5-(4-β-chloroethyl-                                                             yellowish                                         nyl)-ethyl)-amine hydro-                                                                   sulfonyl)-butyrylamino-                                                                      red                                               chloride     benzene-2-sulfonic acid                                       __________________________________________________________________________

EXAMPLE 2

31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid aredissolved in 100 parts of water under neutral conditions. This solutionis added dropwise in the course of 10 minutes to a mixture of 200 partsof ice and water, 18.5 parts of 2,4,6-trichloro-1,3,5-triazine and 10parts of 37% hydrochloric acid. The reaction mixture is held at pH 1.5until the condensation has ended by continuously adding 2N sodiumhydroxide solution.

This intermediate is coupled at 0° to 10° C. and pH 1.0 with 28.1 partsof diazotised 1-amino-4-(β-sulfatoethylsulfonyl)-benzene. After thecoupling reaction at pH 6.5 has ended, the reaction solution is broughtto pH 8.0.

After the addition of 22.9 parts of β-(β-chloroethylsulfonyl)-ethylaminehydrochloride, the temperature of the reaction mixture is graduallyraised from 5° C. to 20° C., while the reaction mixture is initiallyheld at pH 6.5 and then at pH 8.0 by the continuous addition of 2Nsodium hydroxide solution. After the condensation and eliminationreaction has ended at pH 10.0 and 20° C., the resulting reactive dye ofthe formula ##STR22## is salted out by sprinkling in potassium chlorideat pH 7.0, is filtered off and is dried in vacuo. It dyes cotton in redshades.

The dyes in Table 1 can also be synthesised analogously to this variantof the preparation.

EXAMPLE 3

16.0 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid aredissolved in 400 ml of water under neutral conditions, and the solutionis cooled down to 0° to 5° C. 7.1 parts of2,4,6-trifluoro-1,3,5-triazine are added dropwise at this temperatureand pH 4.5 in the course of 15 minutes, during which the pH of thereaction solution is held acid to congo red by the simultaneous additionof 2N sodium hydroxide solution. After the addition of 11.4 parts ofβ-(β-chloroethylsulfonyl)-ethylamine hydrochloride, the reaction mixtureis initially held briefly at pH 6.0 and then at pH 8.0 by the continuousaddition of 2N sodium hydroxide solution while the temperature is raisedfrom 20° to 25° C. in the course of 2 to 3 hours. After the condensationand elimination reaction has ended this dye intermediate is coupled at0° to 10° C. and pH 6.0 with 14.1 L parts of diazotised1-amino-(4-(β-sulfatoethylsulfonyl)-benzene. After the coupling reactionhas ended at pH 6.5, the reaction mixture is held at pH 9.0 at 20° C. bythe continuous addition of 2N sodium hydroxide solution until thecomplete elimination is indicated by chromatography. Thereafter thereaction mixture is clarified at pH 6.5 and the synthesised reactive dyeof the formula ##STR23## is salted out by sprinkling in sodium chloride,is filtered off and is dried in vacuo. It dyes cotton in red shades.

Other useful reactive dyes which dye cotton in the hues given in column4 of Table 2 are obtained when, as in Example 3,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is reacted first with2,4,6-trifluoro-1,3,5-triazine and then with the amino compound given incolumn 2 and the diazotised diazo component indicated in column 3 iscoupled onto the coupling component thus obtained. Not in every case isthe coupling followed by an elimination, as described in Example 3.

                                      TABLE 2                                     __________________________________________________________________________                                  Hue on                                          No.                                                                              Amino compound                                                                             Diazo component                                                                             cotton                                          __________________________________________________________________________    1  β-(β-chloroethylsulfonyl)-                                                       1-amino-3-(β-sulfatoethyl-                                                             yellowish                                          ethylamine hydrochloride                                                                   sulfonyl)-benzene                                                                           red                                             2  β-(β-chloroethylsulfonyl)-                                                       1-amino-2-(β-sulfatoethyl-                                                             red                                                ethylamine hydrochloride                                                                   sulfonyl)-benzene                                             3  β-(β-chloroethylsulfonyl)-                                                       1-amino-4-allysulfonyl-                                                                     red                                                ethylamine hydrochloride                                                                   benzene                                                       4  β-(β-chloroethylsulfonyl)-                                                       1-amino-5-(2,3-dibromopro-                                                                  yellowish                                          ethylamine hydrochloride                                                                   pionylamino)-benzene-2-                                                                     red                                                             sulfonic acid                                                 5  Bis-(β-(β-chloroethylsul-                                                        1-amino-4-(β-sulfatoethyl-                                                             red                                                fonyl)-ethyl)-amine                                                                        sulfonyl)-bezene                                                 hydrochloride                                                              6  Bis-(β-(β-chloroethylsul-                                                        1-amino-2-(β-sulfatoethyl-                                                             red                                                fonyl)-ethyl)-amine                                                                        sulfonyl)-benzene                                                hydrochloride                                                              7  Bis-(β-(β-chloroethylsul-                                                        1-amino-4-allysulfonyl-                                                                     red                                                fonyl)-ethyl)-amine                                                                        benzene                                                          hydrochloride                                                              8  Bis-(β-(β-chloroethylsul-                                                        1-amino-5-(2,3-dibromo-                                                                     yellowish                                          fonyl)-ethyl)-amine                                                                        propionylamino)-benzene-                                                                    red                                                hydrochloride                                                                              2-sulfide acid                                                9  Bis-(Bβ-(β-chloroethysul-                                                        1-amino-3-(β-sulfatoethyl-                                                             yellowish                                          fonyl)-ethyl)-amine                                                                        sulfonyl)-benzene                                                                           red                                                hydrochloride                                                              10 3-(βChloroethylsulfonyl)-                                                             1-amino-4-(β-sulfatoethyl-                                                             red                                                propylamine hydrochloride                                                                  sulfonyl)-benzene                                             11 3-(βChloroethylsulfonyl)-                                                             1-amino-3-(β-sulfatoethyl-                                                             yellowish                                          propylamine hydrochloride                                                                  sulfonyl)-benzene                                                                           red                                             12 3-(β-Chloroethylsulfonyl)-                                                            1-amino-2-(β-sulfatoethyl-                                                             red                                                propylamine hydrochloride                                                                  sulfonyl)-benzene                                             13 3-(β-Chloroethylsulfonyl)-                                                            1-amino-5-(2,3-dibromo-                                                                     yellowish                                          propylamine hydrochloride                                                                  propionylamino)-benzene-2-                                                                  red                                                             sulfonic acid                                                 14 4-(β-Chloroethylsulfonyl)-                                                            1-amino-4-(β-sulfatoethyl-                                                             red                                                butylamine hydrochloride                                                                   sulfonyl)-benzene                                             15 4-(β-Chloroethylsulfonyl)-                                                            1-amino-3-(β-sulfatoethyl-                                                             yellowish                                          butylamine hydrochloride                                                                   sulfonyl)-benzene                                                                           red                                             16 4-(β-Chloroethylsulfonyl)-                                                            1-amino-2-(β-sulfatoethyl                                                              red                                                butylamine hydrochloride                                                                   sulfonyl)-benzene                                             17 4-(β-Chloroethylsulfonyl)-                                                            1-amino-5-(2,3-dibromo-                                                                     yellowish                                          butylamine hydrochloride                                                                   propionylamino)-benzene-2-                                                                  red                                                             sulfonic acid                                                 18 β-(β-Chloroethylsulfonyl)-                                                       1-amino-5-(4-(β-chloroethyl-                                                           yellowish                                          ethylamine hydrochloride                                                                   sulfonyl)-butyrylamino)-                                                                    red                                                             benzene-2-sulfonic acid                                       19 Bis-(β-(β-chloroethylsulfo-                                                      1-amino-5-(4-(β-chloroethyl-                                                           yellowish                                          nyl)-ethyl)-amine hydro-                                                                   sulfonyl)-butyrylamino)-                                                                    red                                                chloride     benzene-2-sulfonic acid                                       __________________________________________________________________________

EXAMPLE 4

A mixture of 28.1 parts of diazotised1-amino-4-(β-sulfatoethylsulfonyl)-benzene and 300 parts of water isadded at 0° to 5° C. to 76.5 parts, dissolved in 600 parts of water, ofthe coupling component of the formula ##STR24## (prepared by acidcoupling of diazotised2-(3'-amino-4'-sulfophenylamino)-4-chloro-6-(β-vinylsulfonylethylamino)-1,3,5-triazine,prepared as described hereinafter, onto1-amino-8-hydroxynaphthalene-3,6-disulfonic acid). After the couplingreaction at pH 6.5 has ended, the reaction mixture, at 20° C., is heldat pH 10.0 by the continuous addition of 2N sodium hydroxide solutionuntil the complete elimination is indicated by chromatography.Thereafter of the reaction mixture is clarified at pH 6.5 and thesynthesised dye of the formula ##STR25## is salted out by sprinkling insodium chloride, is filtered off and is dried in vacuo. It dyes cottonin greenish blue shades.

Preparation of2-(3'-amino-4'-sulfophenylamino)-4-chloro-6-(β-vinylsulfonylethylamino)-1,3,5-triazine

18.8 parts of 1,3-diaminobenzene-4-sulfonic acid are dissolved in 100parts of water under neutral conditions. This solution is added dropwisein the course of 10 minutes to a mixture of 200 parts of ice and water,18.5 parts of 2,4,6-trichloro-1,3,5-triazine and 10 parts of 37%hydrochloric acid. The reaction mixture is held at pH 1.5 until thecondensation has ended by the continuous addition of 2N sodium hydroxidesolution. After the addition of 22.9 parts ofβ-(β-chloroethylsulfonyl)-ethylamine hydrochloride, the temperature ofthe reaction mixture is gradually raised from 5° C. to 20° C. while thereaction mixture is initially held at pH 6.5 and then at pH 8.0 by thecontinuous addition of 2N sodium hydroxide solution. After thecondensation and elimination reaction has ended, this reaction mixtureis used directly for the acid coupling in Example 4.

Other useful reactive dyes which dye cotton in the hues indicated incolumn 4 of Table 3 are obtained when, as in Example 4, the diazotiseddiazo component indicated in column 2 is coupled under acid conditionsonto the 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and thediazotised diazo component indicated in column 3 is coupled onto themonoazo compound obtained. Not in every case is the coupling reactionfollowed by an elimination reaction, as described in Example 4.

                                      TABLE 3                                     __________________________________________________________________________                                             Hue on                               No. Diazo component   Diazo component    cotton                               __________________________________________________________________________    1   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-benzene amino)-4-chloro-6-(β-vinyl-                                              sulfonylethylamino)-1,3,5-                                                    triazine                                                2   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4',6'-disulfo-                                                                       navy                                     sulfonyl)-benzene phenylamino)-4-chloro-6-                                                      (β-vinylsulfonylethylamino)-                                             1,3,5-triazine                                          3   1-Amino-4-(β-sulfatoethyl-                                                                 2-(4'-amino-2',5'-disulfo-                                                                       greenish                                 sulfonyl)-benzene phenylamino)-4-chloro-6-                                                                         blue                                                       (β-vinylsulfonylethylamino)-                                             1,3,5-triazine                                          4   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4',6'-disulfo-                                                                       navy                                     sulfonyl)-benzene phenylamino)-4-chloro-6-                                                      (β-(β-chloroethylsulfonyl)-                                         ethylamino)-1,3,5-triazine                              5   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-benzene amino)-4-chloro-6-(bis-(β-                                               vinylsulfonylethyl)-amino)-                                                   1,3,5-triazine                                          6   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-benzene amino)-4-fluoro-6-(β-vinyl-                                              sulfonylethylamino)-1,3,5-                                                    triazine                                                7   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     sulfonyl)-benzene amino)-4-fluoro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           8   1-Amino-4-(β-sulfatoethyl-                                                                 2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 sulfonyl)-benzene amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                                       nylethylamino)-1,3,5-triazine                           9   1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     sulfonyl)-benzene amino)-4-fluoro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          10  1-Amino-4-(β-sulfatoethyl-                                                                 2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-benzene amino)-4-fluoro-6-(bis-(β-                                               vinylsulfonylethyl)-amino)-                                                   1,3,5-triazine                                          11  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-chloro-6-(β-vinylsulfonylethyl-                                        amino)-1,3,5-triazine                                   12  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-chloro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           13  1-Amino-3-(β-sulfato-                                                                      2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 ethylsulfonyl)-benzene                                                                          amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                                       nylethylamino)-1,3,5-triazine                           14  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-chloro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          15  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-chloro-6-(bis-(β-vinylsulfonyl-                                        ethyl)-amino)-1,3,5-triazine                            16  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-fluoro-6-(β-vinylsulfonylethyl-                                        amino)-1,3,5-triazine                                   17  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-fluoro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           18  1-Amino-3-(β-sulfato-                                                                      2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 ethylsulfonyl)-benzene                                                                          amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                                       nylethylamino)-1,3,5-triazine                           19  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-fluoro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          20  1-Amino-3-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-fluoro-6-(bis-(β-vinylsulfonyl-                                        ethyl)-amino)-1,3,5-triazine                            21  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-chloro-6-(β-vinylsulfonylethyl-                                        amino)-1,3,5-triazine                                   22  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-chloro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           23  1-Amino-2-(β-sulfato-                                                                      2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 ethylsulfonyl)-benzene                                                                          amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                                       nylethylamino)-1,3,5-triazine                           24  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-chloro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          25  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-chloro-6-(bis-(β-vinylsulfonyl-                                        ethyl)-amino)-1,3,5-triazine                            26  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-fluoro-6-(β-vinylsulfonylethyl-                                        amino)-1,3,5-triazine                                   27  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-fluoro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           28  1-Amino-2-(β-sulfato-                                                                      2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 ethylsulfonyl)-benzene                                                                          amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                                       nyl-ethylamino)-1,3,5-triazine                          29  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     ethylsulfonyl)-benzene                                                                          amino)-4-fluoro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          30  1-Amino-2-(β-sulfato-                                                                      2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     ethylsulfonyl)-benzene                                                                          4-fluoro-6-(bis-(β-vinylsulfonyl-                                        ethyl)-amino)-1,3,5-triazine                            31  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     nyl-benzene       4-chloro-6-(β-vinylsulfonylethyl-                                        amino)-1,3,5-triazine                                   32  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     nyl-benzene       amino)-4-chloro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           33  1-Amino-4-allylsulfo-                                                                           2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 nyl-benzene       amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                                       nylethylamino)-1,3,5-triazine                           34  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     nyl-benzene       amino)-4-chloro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          35  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     nyl-benzene       4-chloro-6-(bis-(β-vinylsulfonyl-                                        ethyl)-amino)-1,3,5-triazine                            36  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     nyl-benzene       4-fluoro-6-(β-vinylsulfonylethyl-                                        amino)-1,3,5-triazine                                   37  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     nyl-benzene       amino)-4-fluoro-6-(β-vinylsulfo-                                         nylethylamino)-1,3,5-triazine                           38  1-Amino-4-allylsulfo-                                                                           2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 nyl-benzene       amine)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                                       nylethylamino)-1,3,5-triazine                           39  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     nyl-benzene       amino)-4-fluoro-6-(β-(β-chloro-                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          40  1-Amino-4-allylsulfo-                                                                           2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     nyl-benzene       4-fluoro-6-(bis-(β-vinylsulfonyl-                                        ethyl)-amino)-1,3,5-triazine                            41  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-  4-chloro-6-(β-vinylsulfonylethyl-                      benzene-2-sulfonic acid                                                                         amino)-1,3,5-triazine                                   42  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-  amino)-4-chloro-6-(β-vinylsulfo-                       benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           43  1-Amino-5-(2,3-dibromo-                                                                         2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 propionylamino)-  amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                     benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           44  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-  amino)-4-chloro-6-(β-(β-chloro-                   benzene-2-sulfonic acid                                                                         ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          45  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-  4-chloro-6-(bis-(β-vinylsulfonyl-                      benzene-2-sulfonic acid                                                                         ethyl)-amino)-1,3,5-triazine                            46  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-  4-fluoro-6-(β-vinylsulfonylethyl-                      benzene-2-sulfonic acid                                                                         amino)-1,3,5-triazine                                   47  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-  amino)-4-fluoro-6-(β-vinylsulfo-                       benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           48  1-Amino-5-(2,3-dibromo-                                                                         2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 propionylamino)-  amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                     benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           49  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-  amino)-4-fluoro-6-(β-(β-chloro-                   benzene-2-sulfonic acid                                                                         ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          50  1-Amino-5-(2,3-dibromo-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-  4-fluoro-6-(bis-(β-vinylsulfonyl-                      benzene-2-sulfonic acid                                                                         ethyl)-amino)-1,3,5-triazine                            51  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     acryloylamino)-   4-chloro-6-(β-vinylsulfonylethyl-                      benzene-2-sulfonic acid                                                                         amino)-1,3,5-triazine                                   52  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     acryloylamino)-   amino)-4-chloro-6-(β-vinylsulfo-                       benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           53  1-Amino-5-(α-bromo-                                                                       2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 acryloylamino)-   amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                     benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           54  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     acryloylamino)-   amino)-4-chloro-6-(β-(β-chloro-                   benzene-2-sulfonic acid                                                                         ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          55  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     acryloylamino)-   4-chloro-6-(bis-(β-vinylsulfonyl-                      benzene-2-sulfonic acid                                                                         ethyl)-amino)-1,3,5-triazine                            56  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     acryloylamino)-   4-fluoro-6-(β-vinylsulfonylethyl-                      benzene-2-sulfonic acid                                                                         amino)-1,3,5-triazine                                   57  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     acryloylamino)-   amino)-4-fluoro-6-(β-vinylsulfo-                       benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           58  1-Amino-5-(α-bromo-                                                                       2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 acryloylamino)-   amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                     benzene-2-sulfonic acid                                                                         nylethylamino)-1,3,5-triazine                           59  1-Amino-5-(α-bromo-                                                                       2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     acryloylamino)-   amino)-4-fluoro-6-(β-(β-chloro                    benzene-2-sulfonic acid                                                                         ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          60  1-Amino-5-(αbromo                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     acryloylamino)-   4-fluoro-6-(bis-(β-vinylsulfonyl-                      benzene-2-sulfonic acid                                                                         ethyl)-amino)-1,3,5-triazine                            61  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-benzene-                                                                        4-chloro-6-(β-vinylsulfonylethyl-                      2-sulfonic acid   amino)-1,3,5-triazine                                   62  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-benzene-                                                                        amino)-4-chloro-6-(β-vinylsulfo-                       2-sulfonic acid   nylethylamino)-1,3,5-triazine                           63  1-Amino-5-(2,3-dichloro-                                                                        2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 propionylamino)-benzene-                                                                        amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                     2-sulfonic acid   nylethylamino)-1,3,5-triazine                           64  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-benzene                                                                         amino)-4-chloro-6-(β-(β-chloro-                   2-sulfonic acid   ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          65  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-benzene                                                                         4-chloro-6-(bis-(β-vinylsulfonyl-                      2-sulfonic acid   ethyl)-amino)-1,3,5-triazine                            66  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-benzene                                                                         4-fluoro-6-(β-vinylsulfonylethyl-                      2-sulfonic acid   amino)-1,3,5-triazine                                   67  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4'-disulfophenyl)-                                                                   navy                                     propionylamino)-benzene                                                                         amino)-4-fluoro-6-(β-vinylsulfo-                       2-sulfonic acid   nylethylamino)-1,3,5-triazine                           68  1-Amino-5-(2,3-dichloro-                                                                        2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 propionylamino)-benzene                                                                         amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                     2-sulfonic acid   nylethylamino)-1,3,5-triazine                           69  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     propionylamino)-benzene                                                                         amino)-4-fluoro-6-(β-(β-chloro-                   2-sulfonic acid   ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          70  1-Amino-5-(2,3-dichloro-                                                                        2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     propionylamino)-benzene                                                                         4-fluoro-6-(bis-(β-vinylsulfonyl-                      2-sulfonic acid   ethyl)-amino)-1,3,5-triazine                            71  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     amino-benzene-2-sulfo-                                                                          4-chloro-6-(β-vinylsulfonylethyl-                      nic acid          amino)-1,3,5-triazine                                   72  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     amino-benzene-2-sulfo-                                                                          amino)-4-chloro-6-(β-vinylsulfo-                       nic acid          nylethylamino)-1,3,5-triazine                           73  1-Amino-5-chloroacetyl-                                                                         2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 amino-benzene-2-sulfo-                                                                          amino)-4-chloro-6-(β-vinylsulfo-                                                            blue                                     nic acid          nylethylamino)-1,3,5-triazine                           74  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     amino-benzene-2-sulfo-                                                                          amino)-4-chloro-6-(β-(β-chloro-                   nic acid          ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          75  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     amino-benzene-2-sulfo-                                                                          4-chloro-6-(bis-(β-vinylsulfonyl-                      nic acid          ethyl)-amino)-1,3,5-triazine                            76  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     amino-benzene-2-sulfo-                                                                          4-fluoro-6-(β-vinylsulfonylethyl-                      nic acid          amino)-1,3,5-triazine                                   77  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     amino-benzene-2-sulfo-                                                                          amino)-4-fluoro-6-(β-vinylsulfo-                       nic acid          nylethylamino)-1,3,5-triazine                           78  1-Amino-5-chloroacetyl-                                                                         2-(4'-amino-2',5'-disulfophenyl-                                                                 greenish                                 amino-benzene-2-sulfo-                                                                          amino)-4-fluoro-6-(β-vinylsulfo-                                                            blue                                     nic acid          nylethylamino)-1,3,5-triazine                           79  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4',6'-disulfophenyl-                                                                 navy                                     amino-benzene-2-sulfo-                                                                          amino)-4-fluoro-6-(β-(β-chloro-                   nic acid          ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                          80  1-Amino-5-chloroacetyl-                                                                         2-(3'-amino-4'-sulfophenylamino)-                                                                navy                                     amino-benzene-2-sulfo-                                                                          4-fluoro-6-(bis-(β-vinylsulfonyl-                      nic acid          ethyl)-amino)-1,3,5-triazine                            81  2-(3'-Amino-4',6'-disulfo-                                                                      1-amino-4-(β-sulfatoethylsulfo-                                                             greenish                                 nylamino-4-chloro-6-(β-                                                                    nyl)-benzene       blue                                     vinylsulfonylethylamino)-                                                     1,3,5-triazene                                                            82  2-(4'-Amino-2',5'-disulfo-                                                                      1-amino-4-(β-sulfatoethylsulfo-                                                             greenish                                 phenylamino)-4-chloro-6-                                                                        nyl)-benzene       blue                                     (β-vinylsulfonylethyl-                                                   amino)-1,3,5-triazine                                                     83  2-(3'-Amino-4',6'-disulfo-                                                                      1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 phenylamino)-4-chloro-6-                                                                        sulfonyl)-benzene  blue                                     (β-(β-chloroethylsulfonyl)-                                         ethylamino)-1,3,5-triazine                                                84  2-(3'-Amino-4'-sulfophenyl)-                                                                    1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 amino)-4-chloro-6-(bis-(β-                                                                 sulfonyl)-benzene  blue                                     vinylsulfonylethyl)-amino)-                                                   1,3,5-triazine                                                            85  2-(3'-Amino-4'  -sulfophenyl-                                                                   1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 amino)-4-fluoro-6-(β-vinyl-                                                                sulfonyl)-benzene  blue                                     sulfonylethylamino)-1,3,5-                                                    triazine                                                                  86  2-(3'-Amino-4',6'-disulfo-                                                                      1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 phenylamino)-4-fluoro-6-(β-                                                                sulfonyl)-benzene  blue                                     vinylsulfonylethylamino)-                                                     1,3,5-triazine                                                            87  2-(4'-Amino-2',5'-disulfo-                                                                      1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 phenylamino)-4-fluoro-6-(β-                                                                sulfonyl)-benzene  blue                                     vinylsulfonylethylamino)-                                                     1,3,5-triazine                                                            88  2-(3'-Amino-4',6'-disulfo-                                                                      1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 phenylamino)-4-fluoro-6-(β-                                                                sulfonyl)-benzene  blue                                     (β-chloroethylsulfonyl)-                                                 ethylamino)-1,3,5-triazine                                                89  2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-4-(β-sulfatoethyl-                                                                  greenish                                 amino)-4-fluoro-6-(bis(β-                                                                  sulfonyl)-benzene  blue                                     vinylsulfonylethyl)-amino)-                                                   1,3,5-triazine                                                            90  2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-3-( -sulfatoethyl-                                                                       greenish                                 amino)-4-chloro-6-(β-vinyl-                                                                sulfonyl)-benzene  blue                                     sulfonylethylamino)-1,3,5-                                                    triazine                                                                  91  2-(3'-Amino-4',6'-disulfophe-                                                                   1-amino-3-( -sulfatoethyl-                                                                       greenish                                 nylamino)-4-chloro-6-(β-                                                                   sulfonyl)-benzene  blue                                     vinylsulfonylethylamino)-                                                     1,3,5-triazine                                                            92  2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-3-( -sulfatoethyl-                                                                       greenish                                 amino)-4-chloro-6-(β-vinylsulfo-                                                           sulfonyl)-benzene  blue                                     nylethylamino)-1,3,5-triazine                                             93  2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-3-(β-sulfato-                                                                       greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       ethylsulfonyl)-benaene                                                                           blue                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                                            94  2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-3-(β-sulfato-                                                                       greenish                                 amino)-4-chloro-6-(bis(β-vinyl-                                                            ethylsulfonyl)-benaene                                                                           blue                                     sulfonylethyl)-amino)-1,3,5-triazine                                      95  2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-3-(β-sulfato-                                                                       greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          ethylsulfonyl)-benaene                                                                           blue                                     amino)-1,3,5-triazine                                                     96  2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-3-(β-sulfato-                                                                       greenish                                 amino)-4-fluoro-6-(β-vinylsulfo-                                                           ethylsulfonyl)-benaene                                                                           blue                                     nylethylamino)-1,3,5-triazine                                             97  2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-3-(β-sulfato-                                                                       greenish                                 amino)-4-fluoro-6-(β-vinylsulfo-                                                           ethylsulfonyl)-benaene                                                                           blue                                     nylethylamino)-1,3,5-triazine                                             98  2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-3-(β-sulfato-                                                                       greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       ethylsulfonyl)-benaene                                                                           blue                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                                            99  2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-3-(β-sulfato-                                                                       greenish                                 4-fluoro-6-(bis(β-vinylsulfonyl-                                                           ethylsulfonyl)-benaene                                                                           blue                                     ethyl)-amino)-1,3,5-triazine                                              100 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-2-(β-sulfato-                                                                       greenish                                 4-chloro-6-(β-vinylsulfonylethyl-                                                          ethylsulfonyl)-benzene                                                                           blue                                     amino)-1,3,5-triazine                                                     101 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-chloro-6-(β-vinylsulfo-                                                           ethylsulfonyl)-benzene                                                                           blue                                     nylethylamino)-1,3,5-triazine                                             102 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        ethylsulfonyl)-benzene                                                                           blue                                     ethylamino)-1,3,5-triazine                                                103 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       ethylsulfonyl)-benzene                                                                           blue                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                                            104 2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-chloro-6-(bis-(β-vinyl-                                                           ethylsulfonyl)-benzene                                                                           blue                                     sulfonylethyl)-amino)-1,3,5-triazine                                      105 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-2-(β-sulfato-                                                                       greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          ethylsulfonyl)-benzene                                                                           blue                                     amino)-1,3,5-triazine                                                     106 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-fluoro-6-(β-vinylsulfo-                                                           ethylsulfonyl)-benzene                                                                           blue                                     nylethylamino)-1,3,5-triazine                                             107 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-fluoro-6-(β-vinylsulfo-                                                           ethylsulfonyl)-benzene                                                                           blue                                     nylethylamino)-1,3,5-triazine                                             108 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-2-(β-sulfato-                                                                       greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       ethylsulfonyl)-benzene                                                                           blue                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                                            109 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-2-(β-sulfato-                                                                       greenish                                 4-fluoro-6-(bis-(β-vinylsulfonyl-                                                          ethylsulfonyl)-benzene                                                                           blue                                     ethyl)-amino)-1,3,5-triazine                                              110 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-4-allylsulfo-                                                                            greenish                                 4-chloro-6-(β-vinylsulfonylethyl-                                                          nyl benzene        blue                                     amino)-1,3,5-triazine                                                     111 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        nyl benzene        blue                                     ethylamino)-1,3,5-triazine                                                112 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-chloro-6-(β-vinylsulfo-                                                           nyl benzene        blue                                     nylethylamino)-1,3,5-triazine                                             113 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       nyl benzene        blue                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                                            114 2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-chloro-6-(bis-(β-vinyl-                                                           nyl benzene        blue                                     sulfonylethyl)-amino)-1,3,5-triazine                                      115 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-4-allylsulfo-                                                                            greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          nyl benzene        blue                                     amino)-1,3,5-triazine                                                     116 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        nyl benzene        blue                                     ethylamino)-1,3,5-triazine                                                117 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        nyl benzene        blue                                     ethylamino)-1,3,5-triazine                                                118 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-4-allylsulfo-                                                                            greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       nyl benzene        blue                                     ethylsulfonyl)-ethylamino)-                                                   1,3,5-triazine                                                            119 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-4-allylsulfo-                                                                            greenish                                 4-fluoro-6-(bis(β-vinylsulfonyl-                                                           nyl benzene        blue                                     ethyl)-amino)-1,3,5-triazine                                              120 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(2,3-dibromo-                                                                          greenish                                 4-chloro-6-(β-vinylsulfonylethyl-                                                          propionylamino)-benzene-                                                                         blue                                     amino)-1,3,5-triazine                                                                           2-sulfonic acid                                         121 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-chloro-6-(β-vinylsulfo-                                                           propionylamino)-benzene-                                                                         blue                                     nylethylamino)-1,3,5-triazine                                                                   2-sulfonic acid                                         122 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        propionylamino)-benzene-                                                                         blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         123 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       propionylamino)-benzene-                                                                         blue                                     ethylsulfonyl)-ethylamino)-                                                                     2-sulfonic acid                                             1,3,5-triazine                                                            124 2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-chloro-6-(bis-(β-vinyl-                                                           propionylamino)-benzene-                                                                         blue                                     sulfonylethyl)-amino)-1,3,5-triazine                                                            2-sulfonic acid                                         125 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(2,3-dibromo-                                                                          greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          propionylamino)-benzene-                                                                         blue                                     amino)-1,3,5-triazine                                                                           2-sulfonic acid                                         126 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        propionylamino)-benzene-                                                                         blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         127 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        propionylamino)-benzene-                                                                         blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         128 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-dibromo-                                                                          greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       propionylamino)-benzene-                                                                         blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               2-sulfonic acid                                             triazine                                                                  129 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(2,3-dibromo-                                                                          greenish                                 4-fluoro-6-(bis-(β-vinylsulfonyl-                                                          propionylamino)-benzene-                                                                         blue                                     ethyl)-amino)-1,3,5-triazine                                                                    2-sulfonic acid                                         130 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(α-bromo-                                                                        greenish                                 4-chloro-6-(β-vinylsulfonylethyl-                                                          acryloylamino)-benzene-                                                                          blue                                     amino)-1,3,5-triazine                                                                           2-sulfonic acid                                         131 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        acryloylamino)-benzene-                                                                          blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         132 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        acryloylamino)-benzene-                                                                          blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         133 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       acryloylamino)-benzene-                                                                          blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               2-sulfonic acid                                             triazine                                                                  134 2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-chloro-6-(bis-(β-vinyl-                                                           acryloylamino)-benzene-                                                                          blue                                     sulfonylethyl)-amino)-1,3,5-triazine                                                            2-sulfonic acid                                         135 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(α-bromo-                                                                        greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          acryloylamino)-benzene-                                                                          blue                                     amino)-1,3,5-triazine                                                                           2-sulfonic acid                                         136 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        acryloylamino)-benzene-                                                                          blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         137 2-(4' -Amino-2',5'-disulfophenyl-                                                               1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        acryloylamino)-benzene-                                                                          blue                                     ethylamino)-1,3,5-triazine                                                                      2-sulfonic acid                                         138 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(α-bromo-                                                                        greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       acryloylamino)-benzene-                                                                          blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               2-sulfonic acid                                             triazine                                                                  139 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(α-bromo-                                                                        greenish                                 4-fluoro-6-(bis(β-vinylsulfonyl-                                                           acryloylamino)-benzene-                                                                          blue                                     ethyl)-amino)-1,3,5-triazine                                                                    2-sulfonic acid                                         140 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(2,3-di- greenish                                 4-chloro-6-(βvinylsulfonylethyl-                                                           chloropropionylamino)-                                                                           blue                                     amino)-1,3,5-triazine                                                                           benzene-2-sulfonic acid                                 141 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-di- greenish                                 amino)-4-chloro-6-(β-vinylsulfo-                                                           chloropropionylamino)-                                                                           blue                                     nylethylamino)-1,3,5-triazine                                                                   benzene-2-sulfonic acid                                 142 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-(2,3-di- greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        chloropropionylamino)-                                                                           blue                                     ethylamino)-1,3,5-triazine                                                                      benzene-2-sulfonic acid                                 143 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-di- greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       chloropropionylamino)-                                                                           blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               benzene-2-sulfonic acid                                     triazine                                                                  144 2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-5-(2,3-di- greenish                                 amino)-4-chloro-6-(bis-(β-vinyl-                                                           chloropropionylamino)-                                                                           blue                                     sulfonylethyl)-amino)-1,3,5-triazine                                                            benzene-2-sulfonic acid                                 145 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(2,3-di- greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          chloropropionylamino)-                                                                           blue                                     amino)-1,3,5-triazine                                                                           benzene-2-sulfonic acid                                 146 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-di- greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        chloropropionylamino)-                                                                           blue                                     ethylamino)-1,3,5-triazine                                                                      benzene-2-sulfonic acid                                 147 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-(2,3-di- greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        chloropropionylamino)-                                                                           blue                                     ethylamino)-1,3,5-triazine                                                                      benzene-2-sulfonic acid                                 148 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(2,3-di- greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       chloropropionylamino)-                                                                           blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               benzene-2-sulfonic acid                                     triazine                                                                  149 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(2,3-di- greenish                                 4-fluoro-6-(bis-(β-vinylsulfonyl-                                                          chloropropionylamino)-                                                                           blue                                     ethyl)-amino)-1,3,5-triazine                                                                    benzene-2-sulfonic acid                                 150 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-chloroacetyl-                                                                          greenish                                 4-chloro-6-(β-vinylsulfonylethyl-                                                          amino-benzene-2-   blue                                     amino)-1,3,5-triazine                                                                           sulfonic acid                                           151 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        amino-benzene-2-   blue                                     ethylamino)-1,3,5-triazine                                                                      sulfonic acid                                           152 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-chloro-6-(β-vinylsulfonyl-                                                        amino-benzene-2-   blue                                     ethylamino)-1,3,5-triazine                                                                      sulfonic acid                                           153 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-chloro-6-(β-(β-chloro-                                                       amino-benzene-2-   blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               sulfonic acid                                               triazine                                                                  154 2-(3'-Amino-4'-sulfophenyl-                                                                     1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-chloro-6-(bis-(β-vinyl-                                                           amino-benzene-2-   blue                                     sulfonylethyl)-amino)-1,3,5-                                                                    sulfonic acid                                               triazine                                                                  155 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-chloroacetyl-                                                                          greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          amino-benzene-2-   blue                                     amino)-1,3,5-triazine                                                                           sulfonic acid                                           156 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-fluoro-6-(β -vinylsulfonyl-                                                       amino-benzene-2-   blue                                     ethylamino)-1,3,5-triazine                                                                      sulfonic acid                                           157 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-fluoro-6-(β-vinylsulfonyl-                                                        amino-benzene-2-   blue                                     ethylamino)-1,3,5-triazine                                                                      sulfonic acid                                           158 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-chloroacetyl-                                                                          greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       amino-benzene-2-   blue                                     ethylsulfonyl)-ethylamino)-1,3,5-                                                               sulfonic acid                                               triazine                                                                  159 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-chloroacetyl-                                                                          greenish                                 4-fluoro-6-(bis-(β-vinylsulfonyl-                                                          amino-benzene-2-   blue                                     ethyl)-amino)-1,3,5-triazine                                                                    sulfonic acid                                           160 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-amino-4'-sulfophe-                                                                         navy                                     sulfonyl)-butyrylamino)-benzene-                                                                nylamino)-4-chloro-6-(β-                               2-sulfonic acid   vinylsulfonylethylamino)-                                                     1,3,5-triazine                                          161 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-amino-4',6'-disulfo-                                                                       navy                                     sulfonyl)-butyrylamino)-benzene-                                                                phenylamino)-4-chloro-6-                                    2-sulfonic acid   (β-vinylsulfonylethyl-                                                   amino)-1,3,5-triazine                                   162 1-Amino-5-(4-(β-chloroethyl-                                                               2-(4'-amino-2',5'-disul-                                                                         greenish                                 sulfonyl)-butyrylamino)-benzene-                                                                fophenylamino)-4-chloro-                                                                         blue                                     2-sulfonic acid   6-(β-vinylsulfonylethyl-                                                 amino)-1,3,5-triazine                                   163 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-Amino-4',6'-disul-                                                                         navy                                     sulfonyl)-butyrylamino)-benzene-                                                                fophenylamino)-4-chloro-                                    2-sulfonic acid   6-(β-(β-chloroethylsulfo-                                           nyl)-ethylamino)-1,3,5-                                                       triazine                                                164 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-butyrylamino)-ben-                                                                    amino)-4-chloro-6-(bis-(β-                             zene-2-sulfonic acid                                                                            vinylsulfonylethyl)-amino)-                                                   1,3,5-triazine                                          165 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-butyrylamino)-ben-                                                                    amino)-4-fluoro-6-(β-vinyl-                            zene-2-sulfonic acid                                                                            sulfonylethylamino)-1,3,5-                                                    triazine                                                166 1-Amino-5-(4-(β  -chloroethyl-                                                             2-(3'-amino-4',6'-disulfo-                                                                       navy                                     sulfonyl)-butyrylamino)-ben-                                                                    phenylamino)-4-fluoro-6-(β-                            zene-2-sulfonic acid                                                                            vinylsulfonylethylamino)-                                                     1,3,5-triazine                                          167 1-Amino-5-(4-(β-chloroethyl-                                                               2-(4'-amino-2',5'-disulfo-                                                                       greenish                                 sulfonyl)-butyrylamino)-ben-                                                                    phenylamino)-4-fluoro-6-(β-                                                                 blue                                     zene-2-sulfonic acid                                                                            vinylsulfonylethylamino)-                                                     1,3,5-triazine                                          168 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-amino-4',6'-disulfo-                                                                       navy                                     sulfonyl)-butyrylamino)-ben-                                                                    phenylamino)-4-fluoro-6-(β-(β-                    zene-2-sulfonic acid                                                                            chloroethylsulfonyl)-ethyl-                                                   amino)-1,3,5-triazine                                   169 1-Amino-5-(4-(β-chloroethyl-                                                               2-(3'-amino-4'-sulfophenyl-                                                                      navy                                     sulfonyl)-butyrylamino)-                                                                        amino)-4-fluoro-6-(bis-(β-                             benzene-2-sulfonic acid                                                                         vinylsulfonylethyl)-amino)-                                                   1,3,5-triazine                                          170 2-(3'-Amino-4'-sulfophenyl-                                                                     1-Amino-5-(4-(β-chloroethyl-                                                                greenish                                 amino)-4-chloro-6-(β-vinyl-                                                                sulfonyl)-butyrylamino)-                                                                         blue                                     sulfonylethylamino)-1,3,5-                                                                      benzene-2-sulfonic acid                                     triazine                                                                  171 2-(3'-Amino-4',6'-disulfo-                                                                      1-Amino-5-(4-(β-chloroethyl-                                                                greenish                                 phenylamino)-4-chloro-6-(β-                                                                sulfonyl)-butyrylamino)-                                                                         blue                                     vinylsulfonylethylamino)-                                                                       benzene-2-sulfonic acid                                     1,3,5-triazine                                                            172 2-(4'-Amino-2',5'-disulfo-                                                                      1-Amino-5-(4-(β-chloroethyl-                                                                greenish                                 phenylamino)-4-chloro-6-(β-                                                                sulfonyl)-butyrylamino)-                                                                         blue                                     vinylsulfonylethylamino)-                                                                       benzene-2-sulfonic acid                                     1,3,5-triazine                                                            173 2-(3'-Amino-4',6'-disulfo-                                                                      1-Amino-5-(4-(β-chloroethyl-                                                                greenish                                 phenylamino)-4-chloro-6-(β-                                                                sulfonyl)-butyrylamino)-                                                                         blue                                     (β-chloroethylsulfonyl)-ethyl-                                                             benzene-2-sulfonic acid                                     amino)-1,3,5-triazine                                                     174 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(4-(β-chloro-                                                                     greenish                                 4-chloro-6-(bis-(β-vinylsulfonyl-                                                          ethylsulfonyl)-butyryl-                                                                          blue                                     ethyl)-amino)-1,3,5-triazine                                                                    amino)-benzene-2-                                                             sulfonic acid                                           175 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(4-(β-chloro-                                                                     greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          ethylsulfonyl)-butyryl-                                                                          blue                                     amino)-1,3,5-triazine                                                                           amino)-benzene-2-                                                             sulfonic acid                                           176 2-(3'-Amino-4',6'-disulfophenylamino-                                                           1-amino-5-(4-(β-chloro-                                                                     greenish                                 4-fluoro-6-(β-vinylsulfonylethyl-                                                          ethylsulfonyl)-butyryl-                                                                          blue                                     amino)-1,3,5-triazine                                                                           amino)-benzene-2-                                                             sulfonic acid                                           177 2-(4'-Amino-2',5'-disulfophenyl-                                                                1-amino-5-(4-(β-chloro-                                                                     greenish                                 amino)-4-fluoro-6-(β-vinylsulfo-                                                           ethylsulfonyl)-butyryl-                                                                          blue                                     nylethylamino)-1,3,5-triazine                                                                   amino)-benzene-2-                                                             sulfonic acid                                           178 2-(3'-Amino-4',6'-disulfophenyl-                                                                1-amino-5-(4-(β-chloro-                                                                     greenish                                 amino)-4-fluoro-6-(β-(β-chloro-                                                       ethylsulfonyl)-butyryl-                                                                          blue                                     ethylsulfonyl)-ethylamino)-                                                                     amino)-benzene-2-sulfo-                                     1,3,5-triazine    nic acid                                                179 2-(3'-Amino-4'-sulfophenylamino)-                                                               1-amino-5-(4-(β-chloro-                                                                     greenish                                 4-fluoro-6-(bis-(β-vinylsulfonyl-                                                          ethylsulfonyl)-butyryl-                                                                          blue                                     ethyl)-amino)-1,3,5-triazine                                                                    amino)-benzene-2-sulfo-                                                       nic acid                                                __________________________________________________________________________

EXAMPLE 5

31.9 parts of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid aredissolved in 100 parts of water under neutral conditions. This solutionis added dropwise in the course of 10 minutes to a mixture of 200 partsof ice and water, 18.5 parts of 2,4,6-trichloro-1,3,5-triazine and 10parts of 37% hydrochloric acid. The reaction mixture is held at pH 1.5until the condensation has ended by continuously adding 2N sodiumhydroxide solution.

This intermediate is coupled at 0° to 10° C. and pH 1.0 with 28.1 partsof diazotised 1-amino-4-(β-sulfatoethylsulfonyl)-benzene. After thecoupling reaction at pH 6.5 has ended, the reaction solution is broughtpH 8.0.

After the addition of 22.9 parts of β-(β-chloroethylsulfonyl)-ethylaminehydrochloride, the temperature of the reaction mixture is graduallyraised from 5° C. to 20° C., while the reaction mixture is initiallyheld at pH 6.5 and then at pH 8.0 by the continuous addition of 2Nsodium hydroxide solution. After the condensation and eliminationreaction has ended at pH 10.0 and 20° C., the resulting reactive dye ofthe formula ##STR26## is salted out by sprinkling in potassium chlorideat pH 7.0, is filtered off and is dried in vacuo. It dyes cotton in redshades.

Other useful reactive dyes which dye cotton in the hues indicated incolumn 3 of Table 4 are obtained when1-amino-8-hydroxynaphthalene-4,6-disulfonic acid in the method ofpreparation of Example 5 is replaced by one of the intermediatesindicated in column 2 of Table 4.

                  TABLE 4                                                         ______________________________________                                                                       Hue on                                         No.    Intermediate            cotton                                         ______________________________________                                        1      2-Amino-5-hydroxynaphthalene-7-sulfonic                                                               orange                                                acid                                                                   2      2-Methylamino-5-hydroxynaphthalene-7-                                                                 orange                                                sulfonic acid                                                          3      3-Amino-5-hydroxynaphthalene-7-sulfonic                                                               red                                                   acid                                                                   ______________________________________                                    

EXAMPLE 6

16.0 parts of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid aredissolved in 400 ml of water under neutral conditions, and the solutionis cooled down to 0° to 5° C. 7.1 parts of2,4,6-trifluoro-1,3,5-triazine are added dropwise at this temperatureand pH 4.5 in the course of 15 minutes, during which the pH of thereaction solution is held acid to congo red by the simultaneous additionof 2N sodium hydroxide solution. After the addition of 11.4 parts ofβ-(β-chloroethylsulfonyl)-ethylamine hydrochloride, the reaction mixtureis initially held briefly at pH 6.0 and then at pH 8.0 by the continuousaddition of 2N sodium hydroxide solution while the temperature is raisedfrom 20° to 25° C. in the course of 2 to 3 hours. After the condensationand elimination reaction has ended, this dye intermediate is coupled at0° to 10° C. and pH 6.0 with 14.1 parts of diazotised1-amino-(4-(β-sulfatoethylsulfonyl)-benzene. After the coupling reactionhas ended at pH 6.5, the reaction mixture is held at pH 9.0 at 20° C. bythe continuous addition of 2N sodium hydroxide solution until thecomplete elimination is indicated by chromatography. Thereafter thereaction mixture is clarified at pH 6.5 and the synthesised reactive dyeof the formula ##STR27## is salted out by sprinkling in sodium chloride,is filtered off and is dried in vacuo. It dyes cotton in red shades.

Other useful reactive dyes which dye cotton in the hues indicated incolumn 3 of Table 5 are obtained when1-amino-8-hydroxynaphthalene-4,6-disulfonic acid in the method ofpreparation of Example 6 is replaced by one of the intermediatesindicated in column 2 of Table 5.

                  TABLE 5                                                         ______________________________________                                                                       Hue on                                         No.    Intermediate            cotton                                         ______________________________________                                        1      2-Amino-5-hydroxynaphthalene-7-sulfonic                                                               orange                                                acid                                                                   2      2-Methylamino-5-hydroxynaphthalene-7-                                                                 orange                                                sulfonic acid                                                          3      3-Amino-5-hydroxynaphthalene-7-sulfonic                                                               red                                                   acid                                                                   ______________________________________                                    

DYEING METHOD I

2 parts of the dye obtained in Example 1 are dissolved in 400 parts ofwater; to this solution are added 1,500 parts of a solution whichcontains per liter 53 g of sodium chloride. 100 parts of a cotton fabricare introduced at 40° C. into this dyebath. After 45 minutes 100 partsof a solution which contains per liter 16 g of sodium hydroxide and 20 gof calcined sodium carbonate are added. The temperature of the dyebathis held at 40° C. for a further 45 minutes. The dyed fabric is thenrinsed, is soaped off at the boil with a nonionic detergent for aquarter of an hour, is rinsed once more and is dried.

DYEING METHOD II

2 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water; to this solution are added 1,500 parts of a solutionwhich contains per liter 53 g of sodium chloride. 100 parts of a cottonfabric are introduced at 35° C. into this dyebath. After 20 minutes 100parts of a solution which contains per liter 16 g of sodium hydroxideand 20 g of calcined sodium carbonate are added. The temperature of thedyebath is held at 35° C. for a further 15 minutes. The temperature isthen raised to 60° C. in the course of 20 minutes. The temperature isheld at 60° C. for a further 35 minutes. The fabric is then rinsed, issoaped off at the boil with a nonionic detergent for a quarter of anhour, is rinsed once more and is dried.

DYEING METHOD III

8 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water; to this solution are added 1,400 parts of a solutionwhich contains per liter 100 g of sodium sulfate. 100 parts of a cottonfabric are introduced at 25° C. into this dyebath. After 10 minutes 200parts of a solution which contains per liter 150 g of trisodiumphosphate are added. The temperature of the dyebath is then raised to60° C. in the course of 10 minutes. The temperature is held at 60° C.for a further 90 minutes. The fabric is then rinsed, is soaped off atthe boil with a nonionic detergent for a quarter of an hour, is rinsedonce more and is dried.

DYEING METHOD IV

4 parts of the reactive dye obtained in Example 1 are dissolved in 50parts of water; to this solution are added 50 parts of a solution whichcontains per liter 5 g of sodium hydroxide and 20 g of calcined sodiumcarbonate. The resulting solution is applied to a cotton fabric on apad-mangle in such a way that its weight increases by 70%, and thefabric is then wound onto a beam. In this state the cotton fabric isleft to stand at room temperature for 3 hours. The dyed fabric is thenrinsed, is soaped off at the boil with a nonionic detergent for aquarter of an hour, is rinsed once more and is dried.

DYEING METHOD V

6 parts of the reactive dye obtained in Example 1 are dissolved in 50parts of water; to this solution are added 50 parts of a solution whichcontains per liter 16 g of sodium hydroxide and 0.04 liter of 38° Besodium silicate. The resulting solution is applied to a cotton fabric ona pad-mangle in such a way that its weight increases by 70%, and thefabric is then wound onto a beam. In this state the cotton fabric isleft at room temperature for 10 hours. The dyed fabric is then rinsed,is soaped off at the boil with a nonionic detergent for a quarter of anhour, is rinsed once more and is dried.

DYEING METHOD VI

2 parts of the reactive dye obtained in Example 1 are dissolved in 100parts of water in the presence of 0.5 part of sodiumm-nitrobenzenesulfonate. The resulting solution is used to impregnate acotton fabric in such a way that its weight increases by 75%, and thefabric is then dried. The fabric is then impregnated with a warmsolution at 20° C. which contains per liter 4 g of sodium hydroxide and300 g of sodium chloride, and is squeezed to a 75% weight increase andthe dyeing is steamed at 100° to 102° C. for 30 seconds, is rinsed, issoaped off at the boil with a 0.3% strength solution of a nonionicdetergent for a quarter of an hour, is rinsed and is dried.

PRINTING METHOD I

3 parts of the reactive dye obtained in Example 1 are sprinkled withhigh-speed stirring into 100 parts of stock thickening containing 50parts of 5% strength sodium alginate thickening, 27.8 parts of water, 20parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts ofsodium hydrogencarbonate. The print paste thus obtained is used to printa cotton fabric, which is then dried, and the resulting printed fabricis steamed at 102° C. in saturated steam for 2 minutes. The printedfabric is then rinsed, if desired soaped off at the boil and rinsed oncemore, and is then dried.

PRINTING METHOD II

5 parts of the reactive dye obtained in Example 1 are sprinkled withhigh-speed stirring into 100 parts of a stock thickening containing 50parts of 5% strength sodium alginate thickening, 36.5 parts of water, 10parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 2.5 parts ofsodium hydrogencarbonate. The print paste thus obtained, whose stabilitymeets industrial requirements, is used to print a cotton fabric, whichis then dried, and the resulting printed fabric is steamed at 102° C. insaturated steam for 8 minutes. The printed fabric is then rinsed, ifdesired soaped off at the boil and rinsed once more, and is then dried.

I claim:
 1. A reactive dye of the formula ##STR28## in which D, D₁ andD₂ are each phenylene or naphthylene unsubstituted or substituted byalkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,carboxylic acylamino having 1 to 8 carbon atoms, amino, alkylaminohaving 1 to 4 carbon atoms, phenylamino, N,N-di-β-hydroxyethylamino,N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical,alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano,halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in thealkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms,N-(β-hydroxyethyl)-sulfamoyl, N,N-di-(β-hydroxyethyl)-sulfamoyl,N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl, or sulfo, R₁is hydrogen or C₁₋₄ -alkyl unsubstituted or substituted by halogen,hydroxyl, cyano, C₁₋₄ -alkoxy, methoxycarbonyl, ethoxycarbonyl,sulfamoyl, sulfato, carboxyl or sulfo, R₂ is (1) hydrogen, (2) alkylunsubstituted or substituted by halogen, hydroxyl, cyano, alkoxy,methoxycarbonyl, ethoxycarbonyl, sulfamoyl, sulfato, carboxyl or sulfo,(3) cyclohexyl, (4) phenyl unsubstituted or substituted by methyl,ethyl, methoxy, ethoxy, chlorine, bromine, carboxyl, sulfo orsulfomethyl, or (5) a radical of the formula --alk--SO₂ --Z, wherein alkis C₂₋₆ -alkylene, Y is --SO₂ --Z, --SO₂ --N(R₁)--Z, --N--(R₁)--SO₂ --Z,##STR29## --SO₂ --F, --SO₂ CH₂ --CH═CH₂, --N(R₁)--CO--CBr═CH₂,--N(R₁)--CO--CHBr--CH₂ Br, --N(R₁)--CO--CCl═CH₂, --N(R₁)--CO--CHCl--CH₂Cl, --N(R₁)--CO--CH₂ Cl or --N(R₁)--CO--CH═CH₂, Z is --CH═CH₂ or --CH₂CH₂ --A, A is --OSO₃ H, --SSO₃ H, --OCOCH₃, --OPO₃ H₂, --Cl, --Br or--F, and X is fluorine, chlorine or hydroxyl.
 2. A reactive dyeaccording to claim 1, of the formula ##STR30## in which R₃ is hydrogen,methyl or ethyl, R₄ is hydrogen or --alk--SO₂ --Z, wherein alk is C₂₋₆-alkylene, Y is --SO₂ --Z, Z is --CH═CH₂ or --CH₂ CH₂ --A, A is sulfato,acetoxy, chlorine, phosphato or thiosulfato, and X is fluorine, chlorineor hydroxyl.
 3. A reactive dye according to claim 1, of the formula##STR31## in which R₅ is hydrogen or --alk--SO₂ --Z, wherein alk is C₂₋₆-alkylene, Y is --SO₂ --Z, Z is --CH═CH₂ or --CH₂ CH₂ --A, A is sulfato,acetoxy, chlorine, phosphato or thiosulfato, and X is fluorine, chlorineor hydroxyl.
 4. A reactive dye according to claim 1 of the formula##STR32## in which R₆ is hydrogen or --alk--SO₂ --Z, wherein alk is C₂₋₆-alkylene, Y is --SO₂ --Z, Z is --CH═CH₂ or --CH₂ --CH₂ --A, A issulfato, acetoxy, chlorine, phosphato or thiosulfato, and X is fluorine,chlorine or hydroxyl.
 5. A reactive dye according to claim 4 of theformula ##STR33## in which R₇ is hydrogen or --alk--SO₂ --Z, wherein alkis C₂₋₆ -alkylene, Y is --NH--CO--CHBr--CH₂ --Br, --NH--CO--CBr═CH₂ or--SO₂ --Z, Z is --CH═CH₂ or --CH₂ --CH₂ --A, A is sulfato, acetoxy,chlorine, phosphato or thiosulfato, X is fluorine, chlorine or hydroxyl,and one V is OH the other V is NH₂.
 6. The reactive dye according toclaim 3, of the formula ##STR34##
 7. The reactive dye according to claim3, of the formula ##STR35##
 8. The reactive dye according to claim 3, ofthe formula ##STR36##
 9. The reactive dye according to claim 5, of theformula ##STR37##
 10. The reactive dye according to claim 5, of theformula ##STR38##